15 pages and 5 figures presented at ICONO '98'(Moscow, 1998): Fundamental Aspects of Laser-Matter Interaction, New Nonlinear Optical Materials and Physics of Low-Dimensional Structures
Revivals of optical coherence of molecular photoassociation driven by two ultrashort laser pulses are addressed in the Condon approach. Based on textbook examples and numerical simulation of KrF excimer molecules, a prediction is made about an existence of photon echo on free-bound transitions. Delayed rise and fall of nonlinear polarization in the half-collisions are to be resulted from the resonant quantum states interference whether it be in gas, liquid or solid phases.
We model combined photoassociation and Feshbach resonances in a Bose-Einstein condensate. When the magnetic field is far-off resonance, cross coupling between the two target molecules--enabled by the shared dissociation continuum--leads to an anomalous dispersive shift in the position of laser resonance, as well as unprecedented elimination and enhancement of resonant photoassociation via quantum interference. For off-resonant lasers, a dispersive shift and quantum interference appear similarly in resonant three-body Feshbach losses, except that the Feshbach node is tunable with intensity.
We experimentally investigate various processes present in the photoassociative interaction of an ultracold atomic sample with shaped femtosecond laser pulses. We demonstrate the photoassociation of pairs of rubidium atoms into electronically excited, bound molecular states using spectrally cut femtosecond laser pulses tuned below the rubidium D1 or D2 asymptote. Time-resolved pump-probe spectra reveal coherent oscillations of the molecular formation rate, which are due to coherent transient dynamics in the electronic excitation. The oscillation frequency corresponds to the detun-ing of the sp…
The potential energy curves, permanent and transition dipole moments, and the static dipolar polarizability, of molecular ions composed of one alkali-metal atom and a Strontium ion are determined with a quantum chemistry approach. The molecular ions are treated as effective two-electron systems and are treated using effective core potentials including core polarization, large gaussian basis sets, and full configuration interaction. In the perspective of upcoming experiments aiming at merging cold atom and cold ion traps, possible paths for radiative charge exchange, photoassociation of a cold …
We demonstrate coherent one-color photoassociation of a Bose-Einstein condensate, which results in Rabi oscillations between atomic and molecular condensates. We attain atom-molecule Rabi frequencies that are comparable to decoherence rates by driving photoassociation of atoms in an $^{88}$Sr condensate to a weakly-bound level of the metastable $^{1}S_{0}+^{3}P_{1}$ molecular potential, which has a long lifetime and large Franck-Condon overlap integral with the ground scattering state. Transient shifts and broadenings of the excitation spectrum are clearly seen at short times, and they create …
We report on the high resolution photoassociation spectroscopy of a $^{87}$Rb spin-1 Bose-Einstein condensate to the $1_\mathrm{g} (P_{3/2}) v = 152$ excited molecular states. We demonstrate the use of spin dependent photoassociation to experimentally identify the molecular states and their corresponding initial scattering channel. These identifications are in excellent agreement with the eigenvalues of a hyperfine-rotational Hamiltonian. Using the observed spectra we estimate the change in scattering length and identify photoassociation laser light frequency ranges that maximize the change in…
Quantum coherent control of ultrafast bond making and the subsequent molecular dynamics is crucial for the realization of a new photochemistry, where a shaped laser field is actively driving the chemical system in a coherent way from the thermal initial state of the reactants to the final state of the desired products. We demonstrate here coherent control over the relative yields of Mg$_2$ molecules that are generated via photoassociation and subsequently photodriven into different groups of final states. The strong-field process involves non-resonant multiphoton femtosecond photoassociation o…
We investigate two-frequency photoassociation of a weakly bound molecular state, focusing on a regime where the ac Stark shift is comparable to the halo-state energy. In this "high-intensity" regime, we observe features absent in low-intensity two-frequency photoassociation. We experimentally measure the spectra of $^{86}$Sr atoms coupled to the least bound state of the $^{86}$Sr$_2$ ground electronic channel through an intermediate electronically excited molecular state. We compare the spectra to a simple three-level model that includes a two-frequency drive on each leg of the transition. Wit…
We report on high-resolution two-color photoassociation spectroscopy in the triplet system of magneto-optically trapped 6Li. The absolute transition frequencies have been measured. Strong optical coupling of the bound molecular states has been observed as Autler-Townes splitting in the photoassociation signal. The spontaneous bound-bound transition rate is determined and the molecule formation rate is estimated. The observed lineshapes are in good agreement with the theoretical model.
We theoretically examine Raman photoassociation of a Bose-Einstein condensate, revisiting stimulated Raman adiabatic passage (STIRAP). Due to collisional mean-field shifts, efficient molecular conversion requires strong coupling and low density, either of which can bring about rogue photodissociation to noncondensate modes. We demonstrate explicitly that rogue transitions are negligible for low excited-state fractions and photodissociation that is slower than the STIRAP timescale. Moreover, we derive a reduced-parameter model of collisions, and thereby find that a gain in the molecular convers…
The formation of diatomic molecules with rotational and vibrational coherence is demonstrated experimentally in free-to-bound two-photon femtosecond photoassociation of hot atoms. In a thermal gas at a temperature of 1000 K, pairs of magnesium atoms, colliding in their electronic ground state, are excited into coherent superpositions of bound rovibrational levels in an electronically excited state. The rovibrational coherence is probed by a time-delayed third photon, resulting in quantum beats in the UV fluorescence. A comprehensive theoretical model based on ab initio calculations rationalize…
We present a theoretical analysis of optical pathways for formation of cold Ca($^1$S)Na$^+$($^1$S) molecular ions via an intermediate state. The formation schemes are based on ab initio potential energy curves and transition dipole moments calculated using effective-core-potential methods of quantum chemistry. In the proposed approach, starting from a mixture of cold trapped Ca$^+$ ions immersed into an ultracold gas of Na atoms, (NaCa)$^+$ molecular ions are photoassociated in the excited E$^{1}Σ^+$ electronic state and allowed to spontaneously decay either to the ground electronic state or a…
We report on measurements of the binding energies of several weakly bound vibrational states of the paramagnetic $^{174}$Yb$^{6}$Li molecule in the electronic ground state using two-photon spectroscopy in an ultracold atomic mixture confined in an optical dipole trap. We theoretically analyze the experimental spectrum to obtain an accurate description of the long-range potential of the ground state molecule. Based on the measured binding energies, we arrive at an improved value of the interspecies $s$-wave scattering length $a_{s0}=30$ $a_0$. Employing coherent two-photon spectroscopy we also …
We observe long-range homonuclear diatomic $nD$ Rydberg molecules photoassociated out of an ultracold gas of $^{87}$Rb atoms for 34$\le n \le$40. The measured ground-state binding energies of $^{87}$Rb$(nD-5S_{1/2})$ molecular states are larger than those of their $^{87}$Rb$(nS-5S_{1/2})$ counterparts, showing the dependence of the molecular bond on the angular momentum of the Rydberg atom. We exhibit the transition of $^{87}$Rb$(nD-5S_{1/2})$ molecules from a molecular-binding-dominant regime at low $n$ to a fine-structure-dominant regime at high $n$ [akin to Hund's cases (a) and (c), respect…
We study coherent photoassociation, phenomena analogous to coherent optical transients in few-level systems, which may take place in photoassociation of an atomic Bose-Einstein condensate but not in a nondegenerate gas. We develop a second-quantized Hamiltonian to describe photoassociation, and apply the Hamiltonian both in the momentum representation and in the position representation (field theory). Solution of the two-mode problem including only one mode each for the atomic and molecular condensates displays analogs of Rabi oscillations and rapid adiabatic passage. A classical version of th…
Photoassociation with short laser pulses has been proposed as a technique to create ultracold ground state molecules. A broad-band excitation seems the natural choice to drive the series of excitation and deexcitation steps required to form a molecule in its vibronic ground state from two scattering atoms. First attempts at femtosecond photoassociation were, however, hampered by the requirement to eliminate the atomic excitation leading to trap depletion. On the other hand, molecular levels very close to the atomic transition are to be excited. The broad bandwidth of a femtosecond laser then a…
We report the high resolution photoassociation (PA) spectroscopy of a $^{87}Rb$ Bose-Einstein condensate (BEC) to excited molecular states near the dissociation limit of $5P_{1/2} +5S_{1/2}$ by optical Bragg scattering. Since the detection of optical Bragg scattering in BEC has a high signal-noise ratio, we obtain the high resolution PA spectrum of excited molecular states in the range of $\pm1$ GHz near the dissociation limit of $5P_{1/2} +5S_{1/2}$. We compare the results with the conventional method of trap loss and show that the results agree each other very well. Many interesting phenomen…
Two-photon photoassociation of hot magnesium atoms by femtosecond laser pulses, creating electronically excited magnesium dimer molecules, is studied from first principles, combining \textit{ab initio} quantum chemistry and molecular quantum dynamics. This theoretical framework allows for rationalizing the generation of molecular rovibrational coherence from thermally hot atoms [L. Rybak \textit{et al.}, Phys. Rev. Lett. {\bf 107}, 273001 (2011)]. Random phase thermal wave functions are employed to model the thermal ensemble of hot colliding atoms. Comparing two different choices of basis func…
We present the formation of homonuclear Cs2, K2, and heteronuclear CsK long-range Rydberg molecules in a dual-species magneto-optical trap for 39K and 133Cs by one-photon UV photoassociation. The different ground-state-density dependence of homo- and heteronuclear photoassociation rates and the detection of stable molecular ions resulting from auto-ionization provide an unambiguous assignment. We perform bound-bound millimeter-wave spectroscopy of long-range Rydberg molecules to access molecular states not accessible by one-photon photoassociation. Calculations based on the most recent theoret…
We perform two-photon photoassociation spectroscopy of the heteronuclear CsYb molecule to measure the binding energies of near-threshold vibrational levels of the $X~^{2}Σ_{1/2}^{+}$ molecular ground state. We report results for $^{133}$Cs$^{170}$Yb, $^{133}$Cs$^{173}$Yb and $^{133}$Cs$^{174}$Yb, in each case determining the energy of several vibrational levels including the least-bound state. We fit an interaction potential based on electronic structure calculations to the binding energies for all three isotopologs and find that the ground-state potential supports 77 vibrational levels. We us…
Studies on the interactions between an alkali atom and an alkaline earth ion at low energy are important in the field of cold chemistry. In this paper we, extensively, study the structure, interactions, and dynamics of (MgCs)$^+$ molecular ion. We use an ab initio approach based on the formalism of non-empirical pseudo-potential for Mg$^{2+}$ and Cs$^+$ cores, large Gaussian basis sets and full valence configuration interaction. In this context, the (MgCs)$^+$ cation is treated as an effective two-electron system. Potential energy curves and their spectroscopic constants for the ground and the…
We discuss the dynamics of an atomic Bose-Einstein condensate when pairs of atoms are converted into molecules by single-color photoassociation. Three main regimes are found and it is shown that they can be understood on the basis of time-dependent two-body theory. In particular, the so-called rogue dissociation regime [Phys. Rev. Lett., 88, 090403 (2002)], which has a density-dependent limit on the photoassociation rate, is identified with a transient regime of the two-atom dynamics exhibiting universal properties. Finally, we illustrate how these regimes could be explored by photoassociating…
With ultracold $^{88}$Sr in a 1D magic wavelength optical lattice, we performed narrow line photoassociation spectroscopy near the $^1$S$_0 - ^3$P$_1$ intercombination transition. Nine least-bound vibrational molecular levels associated with the long-range $0_u$ and $1_u$ potential energy surfaces were measured and identified. A simple theoretical model accurately describes the level positions and treats the effects of the lattice confinement on the line shapes. The measured resonance strengths show that optical tuning of the ground state scattering length should be possible without significan…
We show that coherence between two excited ro-vibrational states belonging to the same molecular electronic configuration arises quite naturally due to their interaction with electromagnetic vacuum. For initial preparation of a molecule in the desired ro-vibrational states, we propose to employ the method of ultracold photoassociation. Spontaneous decay of the excited molecule then gives rise to vacuum induced coherence between the excited ro-vibrational states. We demonstrate theoretically an interesting interplay of effects due to vacuum induced coherence and photoassociation. We apply our t…
The electronic structure of the (LiYb)$^+$ molecular ion is investigated with two variants of the coupled cluster method restricted to single, double, and noniterative or linear triple excitations. Potential energy curves for the ground and excited states, permanent and transition electric dipole movements, and long-range interaction coefficients $C_4$ and $C_6$ are reported. The data is subsequently employed in scattering calculations and photoassociation studies. Feshbach resonances are shown to be measurable despite the ion's micromotion in the Paul trap. Molecular ions can be formed in the…
We consider two-color heteronuclear photoassociation of atoms into dipolar molecules in the J=1 electro-vibrational ground state, where a free-ground laser couples atoms directly to the ground state and a free-bound laser couples the atoms to an electronically-excited state. This problem raises an interest because heteronuclear photoassociation from atoms to near-ground state molecules is limited by the small size of the target state. Nevertheless, the addition of the excited state creates a second pathway for creating ground state molecules, leading to quantum interference between direct phot…
By two-color photoassociation of $^{40}$Ca four weakly bound vibrational levels in the Ca$_2$ \Xpot ground state potential were measured, using highly spin-forbidden transitions to intermediate states of the coupled system $^3Π_{u}$ and $^3Σ^+ _{u}$ near the ${^3P_1}$+${^1S_0}$ asymptote. From the observed binding energies, including the least bound state, the long range dispersion coefficients $\mathrm{C}_6, \mathrm{C}_8,\mathrm{C}_{10}$ and a precise value for the s-wave scattering length of 308.5(50)~$a_0$ were derived. From mass scaling we also calculated the corresponding scattering lengt…
The paper investigates cold molecules formation in the photoassociation of two cold atoms by a strong laser pulse applied at short interatomic distances, which lead to a molecular dynamics taking place in the light-induced (adiabatic) potentials. A two electronic states model in the cesium dimer is used to analyse the effects of this strong coupling regime and to show specific results: i) acceleration of the ground state population to the inner zone due to a non-impulsive regime of coupling at short and intermediate interatomic distances; ii) formation of cold molecules in strongly bound level…
We report on the direct optical production and spectroscopy of $^1\mathrm{S}_0\mbox{-}^3\mathrm{P}_0$ molecules with large binding energy using the clock transition of $^{171}\mathrm{Yb}$, and on the observation of the associated orbital Feshbach resonance near $1300\,\mathrm{G}$. We measure the magnetic field dependence of the closed-channel dimer and of the open-channel pair state energy via clock-line spectroscopy in a deep optical lattice. In addition, we show that the free-to-bound transition into the dimer can be made first-order insensitive to the trap depth by choice of the lattice wav…
Photoassociation and the Feshbach resonance are, in principle, feasible means for creating a molecular Bose-Einstein condensate from an already-quantum-degenerate gas of atoms; however, mean-field shifts and irreversible decay place practical constraints on the efficient delivery of stable molecules using either mechanism alone. We therefore propose Feshbach-stimulated Raman photoproduction, i.e., a combination of magnetic and optical methods, as a viable means to collectively convert degenerate atoms into a stable molecular condensate with near-unit efficiency.
We model two bosons in an optical lattice near a Feshbach or photoassociation resonance, focusing on the Bose-Hubbard model in one dimension. Whereas the usual atoms-only theory with a tunable scattering length yields one bound state for a molecular dimer for either attractive or repulsive atom-atom interaction, an atom-molecule theory gives two bound states that may represent attractively and repulsively bound dimers occurring simultaneously. Such unusual molecular physics should be observable for an atom-molecule coupling strength comparable to the width of the dissociation continuum of the …
Collective two-color photoassociation of a freely-interacting 87Rb Bose-Einstein condensate is theoretically examined, focusing on stimulated Raman adiabatic passage (STIRAP) from an atomic to a stable molecular condensate. In particular, Drummond et al. [Phys. Rev. A 65, 063619 (2002); cond-mat/0110578] have predicted that particle-particle interactions can limit the efficiency of collective atom-molecule STIRAP, and that optimizing the laser parameters can partially overcome this limitation. We suggest that the molecular conversion efficiency can be further improved by treating the initial c…
It is possible to tune the scattering length for the collision of ultra-cold 1S0 ground state alkaline-earth atoms using an optical Feshbach resonance. This is achieved with a laser far detuned from an excited molecular level near the frequency of the atomic intercombination 1S0--3P1 transition. Simple resonant scattering theory, illustrated by the example of 40Ca, allows an estimate of the magnitude of the effect. Unlike alkali metal species, large changes of the scattering length are possible while atom loss remains small, because of the very narrow line width of the molecular photoassociati…
We demonstrate that a near-dissociation photoassociation resonance can be used to create a deeply bound molecular sample of ultracold NaCs. To probe the resulting vibrational distribution of the sample, we use a new technique that can be applied to any ultracold molecular system. We utilize a tunable pulsed dye laser to produce efficient spectroscopic scans ($\sim700$ cm$^{-1}$ at a time) in which we observe the $1^{1} Σ^{+}\rightarrow 2^{1}Σ^{+}-2^{3}Π$ vibrational progression, as well as the dissociation limit to the Cs 6$^{2}$P$_{3/2}$ asymptote. We assign $1^{1} Σ^{+}$$(\emph{v}$ = 4, 5, 6…
Long-range metastable molecules consisting of two cesium atoms in high Rydberg states have been observed in an ultracold gas. A sequential three-photon two-color photoassociation scheme was employed to form these molecules in states which correlate to $np(n+1)s$ dissociation asymptotes. Spectral signatures of bound molecular states are clearly resolved at the positions of avoided crossings between long-range van der Waals potential curves. The experimental results are in agreement with simulations based on a detailed model of the long-range multipole-multipole interactions of Rydberg-atom pair…
We investigate the dynamics of molecular photoexcitation by unchirped femtosecond laser pulses using RbCs as a model system. This study is motivated by a goal of optimizing a two-color scheme of transferring vibrationally-excited ultracold molecules to their absolute ground state. In this scheme the molecules are initially produced by photoassociation or magnetoassociation in bound vibrational levels close to the first dissociation threshold. We analyze here the first step of the two-color path as a function of pulse intensity from the low-field to the high-field regime. We use two different a…
Optical molecular clocks promise unparalleled sensitivity to the temporal variation of the electron-to-proton mass ratio and insight into possible new physics beyond the Standard Model. We propose to realize a molecular clock with bosonic $^{174}$Yb$_2$ molecules, where the forbidden $^1$S$_0$$\rightarrow$$^3$P$_0$ clock transition would be induced magnetically. The use of a bosonic species avoids possible complications due to hyperfine structure present in fermionic species. While direct clock line photoassociation would be challenging, weakly bound ground state molecules could be produced by…
We demonstrate photoassociation (PA) of ultracold fermionic $^{87}$Sr atoms. The binding energies of a series of molecular states on the $^1Σ^+_u$ $5s^2\,^1$S$_0+5s5p\,^1$P$_1$ molecular potential are fit with the semiclassical LeRoy-Bernstein model, and PA resonance strengths are compared to predictions based on the known $^1$S$_0+^1$S$_0$ ground state potential. Similar measurements and analysis were performed for the bosonic isotopes $^{84}$Sr and $^{86}$Sr, allowing a combined analysis of the long-range portion of the excited-state potential and determination of the $5s5p\,^1$P$_1$ atomic …
Ultrafast two-dimensional spectroscopy utilizes correlated multiple light-matter interactions for retrieving dynamic features that may otherwise be hidden under the linear spectrum. Its extension to the terahertz regime of the electromagnetic spectrum, where a rich variety of material degrees of freedom reside, remains an experimental challenge. Here we report ultrafast two-dimensional terahertz spectroscopy of gas-phase molecular rotors at room temperature. Using time-delayed terahertz pulse pairs, we observe photon echoes and other nonlinear signals resulting from molecular dipole orientatio…
Ultracold molecules have experienced increasing attention in recent years. Compared to ultracold atoms, they possess several unique properties that make them perfect candidates for the implementation of new quantum-technological applications in several fields, from quantum simulation to quantum sensing and metrology. In particular, ultracold molecules of two-electron atoms (such as strontium or ytterbium) also inherit the peculiar properties of these atomic species, above all the possibility to access metastable electronic states via direct excitation on optical clock transitions with ultimate…
Within the framework of master equation, we study decay dynamics of an atom-molecule system strongly coupled by two photoassociation lasers. Summing over the infinite number of electromagnetic vacuum modes that are coupled to the laser-dressed atom-molecule system, we obtain an integro-differential master equation for the the system's reduced density matrix. The equation is numerically solved to describe system dynamics in the presence of decay. In particular, we discuss correlated spontaneous emission from a pair of electronically excited diatomic ro-vibrational states due to their laser indu…
We report on high-resolution spectroscopy of ultracold fermionic \nak~Feshbach molecules, and identify a two-photon pathway to the rovibrational singlet ground state via a resonantly mixed \Bcres intermediate state. Photoassociation in a $^{23}$Na-$^{40}$K atomic mixture and one-photon spectroscopy on \nak~Feshbach molecules reveal about 20 vibrational levels of the electronically excited \ctrip state. Two of these levels are found to be strongly perturbed by nearby \Bsing states via spin-orbit coupling, resulting in additional lines of dominant singlet character in the perturbed complex {${\r…
